JPH0364485A - Surface treating agent and treating bath for aluminum or aluminum alloy - Google Patents
Surface treating agent and treating bath for aluminum or aluminum alloyInfo
- Publication number
- JPH0364485A JPH0364485A JP1199656A JP19965689A JPH0364485A JP H0364485 A JPH0364485 A JP H0364485A JP 1199656 A JP1199656 A JP 1199656A JP 19965689 A JP19965689 A JP 19965689A JP H0364485 A JPH0364485 A JP H0364485A
- Authority
- JP
- Japan
- Prior art keywords
- ions
- aluminum
- weight
- parts
- surface treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910052782 aluminium Inorganic materials 0.000 title claims abstract description 32
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 title claims description 31
- 229910000838 Al alloy Inorganic materials 0.000 title abstract description 4
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 13
- 150000002500 ions Chemical class 0.000 claims abstract description 10
- 150000002739 metals Chemical class 0.000 claims abstract description 9
- 229910052706 scandium Inorganic materials 0.000 claims abstract description 9
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 9
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 8
- 229910052777 Praseodymium Inorganic materials 0.000 claims abstract description 8
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 7
- 229910052691 Erbium Inorganic materials 0.000 claims abstract description 7
- 229910052688 Gadolinium Inorganic materials 0.000 claims abstract description 7
- 229910052689 Holmium Inorganic materials 0.000 claims abstract description 7
- 229910052765 Lutetium Inorganic materials 0.000 claims abstract description 7
- 229910052772 Samarium Inorganic materials 0.000 claims abstract description 7
- 229910052771 Terbium Inorganic materials 0.000 claims abstract description 7
- 229910052769 Ytterbium Inorganic materials 0.000 claims abstract description 7
- 229910052693 Europium Inorganic materials 0.000 claims abstract description 6
- 229910052775 Thulium Inorganic materials 0.000 claims abstract description 6
- -1 zirconium ions Chemical class 0.000 claims description 27
- 238000004381 surface treatment Methods 0.000 claims description 23
- 229910052731 fluorine Inorganic materials 0.000 claims description 14
- 239000011737 fluorine Substances 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 239000000956 alloy Substances 0.000 claims description 13
- 229910052726 zirconium Inorganic materials 0.000 claims description 12
- 239000012756 surface treatment agent Substances 0.000 claims description 11
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 7
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 7
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 7
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 7
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 7
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 6
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 6
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 6
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 6
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 6
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 6
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 6
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 6
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 25
- 238000009835 boiling Methods 0.000 abstract description 20
- 238000000576 coating method Methods 0.000 abstract description 17
- 239000011248 coating agent Substances 0.000 abstract description 15
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000011282 treatment Methods 0.000 description 18
- 239000003973 paint Substances 0.000 description 12
- 229910021645 metal ion Inorganic materials 0.000 description 11
- 239000000243 solution Substances 0.000 description 10
- 230000000052 comparative effect Effects 0.000 description 9
- 238000000034 method Methods 0.000 description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 229910002651 NO3 Inorganic materials 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 3
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 3
- 229910019142 PO4 Inorganic materials 0.000 description 3
- 235000013361 beverage Nutrition 0.000 description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005096 rolling process Methods 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- GBNDTYKAOXLLID-UHFFFAOYSA-N zirconium(4+) ion Chemical compound [Zr+4] GBNDTYKAOXLLID-UHFFFAOYSA-N 0.000 description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 2
- RGHNJXZEOKUKBD-SQOUGZDYSA-N Gluconic acid Natural products OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 description 2
- 229910000861 Mg alloy Inorganic materials 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000174 gluconic acid Substances 0.000 description 2
- 235000012208 gluconic acid Nutrition 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 230000001954 sterilising effect Effects 0.000 description 2
- 238000004659 sterilization and disinfection Methods 0.000 description 2
- 239000008399 tap water Substances 0.000 description 2
- 235000020679 tap water Nutrition 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910019979 (NH4)2ZrF6 Inorganic materials 0.000 description 1
- KWMLJOLKUYYJFJ-UHFFFAOYSA-N 2,3,4,5,6,7-Hexahydroxyheptanoic acid Chemical compound OCC(O)C(O)C(O)C(O)C(O)C(O)=O KWMLJOLKUYYJFJ-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 229910000676 Si alloy Inorganic materials 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 229910001297 Zn alloy Inorganic materials 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- SNAAJJQQZSMGQD-UHFFFAOYSA-N aluminum magnesium Chemical compound [Mg].[Al] SNAAJJQQZSMGQD-UHFFFAOYSA-N 0.000 description 1
- FJMNNXLGOUYVHO-UHFFFAOYSA-N aluminum zinc Chemical compound [Al].[Zn] FJMNNXLGOUYVHO-UHFFFAOYSA-N 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000002738 chelating agent Substances 0.000 description 1
- KRVSOGSZCMJSLX-UHFFFAOYSA-L chromic acid Substances O[Cr](O)(=O)=O KRVSOGSZCMJSLX-UHFFFAOYSA-L 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000002845 discoloration Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- AWJWCTOOIBYHON-UHFFFAOYSA-N furo[3,4-b]pyrazine-5,7-dione Chemical compound C1=CN=C2C(=O)OC(=O)C2=N1 AWJWCTOOIBYHON-UHFFFAOYSA-N 0.000 description 1
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 239000000976 ink Substances 0.000 description 1
- 238000010409 ironing Methods 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- 239000010452 phosphate Substances 0.000 description 1
- 229940085991 phosphate ion Drugs 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 150000003682 vanadium compounds Chemical class 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
- 150000003755 zirconium compounds Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C22/00—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals
- C23C22/05—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions
- C23C22/06—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6
- C23C22/34—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides
- C23C22/36—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates
- C23C22/361—Chemical surface treatment of metallic material by reaction of the surface with a reactive liquid, leaving reaction products of surface material in the coating, e.g. conversion coatings, passivation of metals using aqueous solutions using aqueous acidic solutions with pH less than 6 containing fluorides or complex fluorides containing also phosphates containing titanium, zirconium or hafnium compounds
Landscapes
- Chemical & Material Sciences (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Chemical Treatment Of Metals (AREA)
Abstract
Description
【発明の詳細な説明】
〔産業上の利用分野〕
本発明は、アルミニウム又はその合金の表面を処理する
ための処理剤及び処理浴に関し、特にアルミニウム又は
その合金からなる飲料缶等の処理に適した処理剤及び処
理浴に関する。Detailed Description of the Invention [Field of Industrial Application] The present invention relates to a treatment agent and a treatment bath for treating the surface of aluminum or its alloy, and is particularly suitable for treating beverage cans made of aluminum or its alloy. The present invention relates to processing agents and processing baths.
アルミニウム又はその合金の防食及び塗装下地の形成を
目的として、化成処理を施すことは、従来から広く行な
われている。その代表的な例として、クロム酸、リン酸
、弗化水素酸を含有する溶液で処理する方法がある。こ
の方法によると、耐洪水黒変性、塗膜との密着性ともに
良好な皮膜を得ることができるが、毒性の高い６価のク
ロムを含有しているため、人体への影響及び廃水処理等
に問題がある。そこで６価のクロムを含まない溶液がこ
れまでに種々開発されている。BACKGROUND ART Chemical conversion treatment has been widely practiced for the purpose of preventing corrosion of aluminum or its alloys and forming a base for painting. A typical example is a method of treatment with a solution containing chromic acid, phosphoric acid, or hydrofluoric acid. According to this method, it is possible to obtain a film with good resistance to flood blackening and adhesion to the paint film, but since it contains highly toxic hexavalent chromium, it has an adverse effect on the human body and has a negative impact on wastewater treatment. There's a problem. Therefore, various solutions that do not contain hexavalent chromium have been developed.
例えば、ジルコニウム、ホスフェート及び有効フッ化物
を含むｐＨが１．５〜４．０のアルミニウム表面処理用
コーティング溶液（特公昭５６−３３４６８号公報）や
、バナジウム化合物と、ジルコニウム化合物又はケイフ
ッ化化合物を含むアルミニウム又はアルミニウム合金の
化成処理液（特開昭５６−１３６９７８号公報）や、ハ
フニウムイオンとフッ素イオンとを含有する酸性水性組
成物（特公昭６０−１３４２７号公報）などが知られて
いる。For example, a coating solution for aluminum surface treatment with a pH of 1.5 to 4.0 containing zirconium, phosphate, and an available fluoride (Japanese Patent Publication No. 33468/1983), and a coating solution containing a vanadium compound, a zirconium compound, or a silicofluoride compound Chemical conversion treatment solutions for aluminum or aluminum alloys (JP-A-56-136978) and acidic aqueous compositions containing hafnium ions and fluorine ions (JP-B-60-13427) are known.
しかしながら、特公昭５６−３３４６８号公報に記載さ
れているコーティング溶液は、新姓液、即ち調製したば
かりの新しい溶液では、十分な性能を示すが、化成処理
を繰り返し、フッ素のエツチングによって溶液中にアル
ミニウムが蓄積するに件ない、殺菌のため沸騰水で処理
する際に、生成皮膜が黒変するという問題が生じ、また
皮膜上に塗布されるペイント、インク、ラッカーなどの
塗膜との密着性が不十分となる。また生成皮膜面の滑り
性が悪いため、この溶液で処理した缶の搬送が円滑に行
えないという問題も生ずる。However, the coating solution described in Japanese Patent Publication No. 56-33468 shows sufficient performance when used as a fresh solution, that is, when it is a freshly prepared solution, but after repeated chemical conversion treatments, fluorine is etched into the solution. Due to the accumulation of aluminum, there is a problem that the resulting film turns black when treated with boiling water for sterilization, and the adhesion of paints, inks, lacquers, etc. becomes insufficient. Another problem arises in that cans treated with this solution cannot be transported smoothly because of the poor slipperiness of the surface of the resulting film.
また、特開昭５６−１３６９７８号公報に記載されてい
る処理液は、比較的高温、長時間の処理（好ましい範囲
として、５０〜８０℃、３〜５分間）を必要とするうえ
、上述の耐沸水黒変性及び塗膜との密着性が不十分であ
る。また生成皮膜が灰色であるため、飲料缶用途のアル
ミニウム又はアルミニウム合金に適用するには不適当で
ある。Furthermore, the treatment liquid described in JP-A-56-136978 requires treatment at a relatively high temperature and for a long time (preferably at 50 to 80°C for 3 to 5 minutes). Resistance to boiling water blackening and adhesion to paint film are insufficient. Furthermore, since the resulting film is gray, it is unsuitable for application to aluminum or aluminum alloys for beverage cans.
さらに、特公昭６０−１３４．２７号公報の組成物も、
耐沸水黒変性及び塗膜密着性が不十分である。Furthermore, the composition of Japanese Patent Publication No. 60-134.27 also
Boiling water blackening resistance and coating adhesion are insufficient.
従って、本発明の目的は、６価クロムの影響を排除する
とともに、前述した従来技術の問題点を解消し、低温、
短時間での処理が可能であり、耐沸水黒変性、塗膜との
密着性及び滑り性に優れた皮膜を形成することができ、
かつ経時変化が少なく、新姓液でなくても上記した特性
を有する皮膜を形成することのできるアルミニウム又は
その合金の表面処理剤及び処理浴を提供することにある
。Therefore, an object of the present invention is to eliminate the influence of hexavalent chromium, solve the problems of the prior art described above, and
It can be processed in a short time and forms a film with excellent boiling water blackening resistance, adhesion to paint films, and slipperiness.
Another object of the present invention is to provide a surface treatment agent and a treatment bath for aluminum or its alloys that have little change over time and can form a film having the above characteristics even if it is not a new liquid.
上記問題点を解決するために鋭意研究の結果、本発明者
は、スカンジウム、イツトリウム、ランタン、プラセオ
ジム、ネオジム、サマリウム、ユーロピウム、ガドリウ
ム、テルビウム、ジスプロシウム、ホルミウム、エルビ
ウム、ツリウム、イッテルビウム、ルテチウムからなる
群から選ばれた１種又は２種以上の金属のイオン、ジル
コニウムイオン、リン酸イオン及び有効フン素イオンを
特定割合で配合させればよいことを発見し、本発明に想
到した。As a result of intensive research to solve the above-mentioned problems, the present inventor discovered that the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium The present inventors have discovered that it is sufficient to mix one or more metal ions selected from the following, zirconium ions, phosphate ions, and effective fluoride ions in specific proportions, and have come up with the present invention.
すなわち、本発明のアルミニウム又はその合金の表面処
理剤は、スカンジウム、イツトリウム、ランタン、プラ
セオジム、ネオジム、サマリウム、ユーロピウム、ガド
リウム、テルビウム、ジスプロシウム、ホルミウム、エ
ルビウム、ツリウム、イッテルビウム、ルテチウムから
なる群から選ばれた１種又は２種以上の金属のイオン１
０〜１０００重量部に対して、ジルコニウムイオンを１
０〜５００重量部、リン酸イオンを１０〜５００重量部
、及び有効フッ素イオンを１〜５０重量部の割合で含有
することを特徴どする。That is, the surface treatment agent for aluminum or its alloy of the present invention is selected from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. Ions of one or more metals 1
1 zirconium ion per 0 to 1000 parts by weight
It is characterized by containing 0 to 500 parts by weight, 10 to 500 parts by weight of phosphate ions, and 1 to 50 parts by weight of effective fluorine ions.
また本発明のアルミニウム又はその合金の表面処理浴は
、スカンジウム、イツトリウム、ランタン、プラセオジ
ム、ネオジム、サマリウム、ユーロピウム、ガドリウム
、テルビウム、ジスプロシウム、ホルミウム、エルビウ
ム、ツリウド、イッテルビウム、ルテチウムからなる群
から選ばれた↓種又は２種以上の金属のイオン１０〜Ｌ
ＯＯＯｐｐｍ、ジルコニウムイオンを１０〜５００ｐｐ
ｍ、 リン酸イオンを１０〜５０［］ｐｐｍ、有効フ
ッ素イオンを１〜５０ｐｐｍ含み、ｐＨが１．８〜４．
０であることを特徴とする。Further, the surface treatment bath for aluminum or its alloy of the present invention is selected from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thuriud, ytterbium, and lutetium. ↓Species or 2 or more metal ions 10~L
OOOppm, 10-500pp of zirconium ions
m, contains 10 to 50 ppm of phosphate ions, 1 to 50 ppm of effective fluorine ions, and has a pH of 1.8 to 4.
It is characterized by being 0.
以下本発明の詳細な説明するが、以下の説明においては
、スカンジウム、イツトリウム、ランタン、プラセオジ
ム、ネオジム、サマリウム、ユロビウム、ガドリウム、
テルビウム、ジスプロシウム、ホルミウム、エルビウム
、ツリウム、イツテルビウム、ルテチウムからなる群か
ら選ばれた１種又は２種以上の金属を便宜上「選択され
た金属」、それらのイオンを「選択された金属イオン」
と呼ぶ。The present invention will be described in detail below. In the following description, scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, eurobium, gadolinium,
For convenience, one or more metals selected from the group consisting of terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium are referred to as "selected metals," and their ions are referred to as "selected metal ions."
It is called.
本発明においては、上記選択された金属中、スカンジウ
ム、イツトリウム、ランタン、プラセオジム及びネオジ
ムが特に好ましい。In the present invention, scandium, yttrium, lanthanum, praseodymium and neodymium are particularly preferred among the metals selected above.
本発明の表面処理剤はアルミニウム又はその合金の表面
処理に用いる物質を所定の割合で含有するもので、適当
な濃度となるように薄めて処理浴とする。その中に含ま
れている選択された金属イオンは１０〜１０００重量部
（表面処理浴中の濃度としては選択された金属イオン１
０〜１１０００ｐｐ 、以下同じ）である。選択された
金属イオン含有量が１０重量部（１０ｐｐｍ）未満では
、殺菌のために沸とう水で処理した際に、生成皮膜が黒
変し、耐沸水黒変性が劣ったものとなり、更には、ペイ
ント等の塗膜との密着性、滑り性が悪化する。選択され
た金属イオンを１０００重量部（ｌｏｏＯｐｐｍ）を越
えて添加しても、効果はそれ以上向上しないので、経済
性を考慮すると１０００重量部（１０１０００ｐｐで十
分である。好ましい範囲は、２５〜５００重量部（２５
〜５００ｐｐｍ）、特に２５〜２００重量部（２５〜２
００ｐｐｍ）である。The surface treatment agent of the present invention contains substances used for surface treatment of aluminum or its alloys in a predetermined ratio, and is diluted to an appropriate concentration to form a treatment bath. The selected metal ions contained therein are 10 to 1000 parts by weight (the concentration in the surface treatment bath is 1 part by weight of the selected metal ions).
0 to 11000pp (the same applies hereinafter). If the selected metal ion content is less than 10 parts by weight (10 ppm), the resulting film will turn black when treated with boiling water for sterilization, resulting in poor boiling water blackening resistance, and furthermore, Adhesion and slipperiness with coatings such as paint deteriorate. Even if more than 1000 parts by weight (looOppm) of the selected metal ion is added, the effect will not be improved any further, so 1000 parts by weight (101000ppm) is sufficient considering economic efficiency.The preferred range is 25 to 500 parts by weight (looOppm). Parts by weight (25
~500 ppm), especially 25-200 parts by weight (25-2
00ppm).
選択された金属イオンの供給源としては、それぞれの金
属の硝酸塩、硫酸塩、ハロゲン化物等の可溶性塩ならば
いずれも適用できるが、特に硝酸塩が好ましい。As the source of the selected metal ions, any soluble salt of the respective metal such as nitrate, sulfate, or halide can be used, but nitrate is particularly preferred.
また、本発明の表面処理剤（表面処理浴）は、↑０〜５
００重量部（１０〜５ｏｏｐｐｍ＞ 、好ましくは２０
〜１００重量部（２０〜１０１００ｐｐのジルコニウム
イオンを含んでいる。ジルコニウムイオン含有量が１０
重量部（１０ｐｐｍ）未満では、皮膜生成速度が極端に
低くなり、満足な皮膜が形成されない。しかしジルコニ
ウムイオンを５００重量部（５００ｐｐｍ）を越えて添
加しても、ジルコニウム添加の効果はそれほど向上せず
、経済性を考慮すると５００重量部（５００ｐｐｍ）で
十分である。In addition, the surface treatment agent (surface treatment bath) of the present invention is ↑0 to 5
00 parts by weight (10-5ooppm>, preferably 20
~100 parts by weight (contains 20 to 10100 pp of zirconium ions. Zirconium ion content is 10
If it is less than 10 ppm by weight, the film formation rate will be extremely low and a satisfactory film will not be formed. However, even if more than 500 parts by weight (500 ppm) of zirconium ions are added, the effect of the addition of zirconium does not improve much, and 500 parts by weight (500 ppm) is sufficient considering economic efficiency.
ジルコニウムイオンの供給源としては、Ｈ２Ｚ ｒ Ｆ
ｅ、（ＮＨ４） ２ＺｒＦ６、Ｎａ２ＺｒＦｓ 、Ｋ
２ＺｒＦ６、Ｚｒ （Ｎｏ３） ４、Ｚｒ０（ＮＯ３）
２ 、Ｚｒ （ＮＯ４） ２、ＺｒＯ３Ｏ２などを挙
げることができ、特に（ＮＩｌ４）２ＺｒＦ６が好まし
い。As a source of zirconium ions, H2Z r F
e, (NH4)2ZrF6, Na2ZrFs, K
2ZrF6, Zr (No3) 4, Zr0 (NO3)
2, Zr(NO4)2, ZrO3O2, etc., and (NIl4)2ZrF6 is particularly preferred.
更に、本発明の表面処理剤（表面処理浴）は、１０〜５
００重量部（１０〜５００ｐｐｍ） 、好ましくは２５
〜２００重量部（２５〜２００ｐｐｍ）のリン酸イオン
を含んでいる。リン酸イオンの含有量が１０重量部（１
０ｐｐｍ）未満では、塗膜との密着性が悪化し、また５
００重量部（５００ｐｐｍ）を越えると耐沸水黒変性、
塗膜との密着性が悪化するうえ、Ｚｒ”Ｍ−ＡＩ−ＰＯ
６（ここでＭは選択された金属を示す、以下同じ）の沈
澱が生成する恐れが生じてくる。Furthermore, the surface treatment agent (surface treatment bath) of the present invention has a
00 parts by weight (10-500 ppm), preferably 25
Contains ~200 parts by weight (25-200 ppm) of phosphate ions. The content of phosphate ions is 10 parts by weight (1
If the amount is less than 0 ppm), the adhesion with the paint film will deteriorate;
If it exceeds 00 parts by weight (500 ppm), boiling water blackening occurs.
In addition to deteriorating the adhesion with the paint film, Zr"M-AI-PO
There is a possibility that a precipitate of No. 6 (herein M indicates a selected metal, the same applies hereinafter) may be formed.
リン酸イオンの供給源としては、Ｈ，ｒＰＯ，、Ｎａ８
２ＰＯ，、（ＮＨ４）Ｈ２ＰＯ，などを挙げることがで
き、なかでもＨ、Ｐ Ｏ４が好適である。As a source of phosphate ions, H, rPO, Na8
2PO, (NH4)H2PO, etc., among which H and PO4 are preferred.
本発明の表面処理剤（表面処理浴）は、１〜５０重量部
（１〜５０ｐｐｍ）、好ましくは３〜２０重量部（３〜
２０ｐｐｍ）の有効フッ素イオンを含んでいる。有効フ
ッ素イオンの含有量が１重量部（１ｐｐｍ）未満では、
アルミニウムのエツチング反応がほとんど起こらず、皮
膜が生成しない。一方、５０重量部（５０ｐｐｍ）を越
えると、皮膜生成速度よりもアルミニウムのエツチング
速度の方が大きくなって、皮膜が生成し難くなる。また
皮膜が生成したとしても、耐沸水黒変性、塗膜との密着
性が悪化する。ここで、有効フッ素イオンとは遊離のフ
ッ素イオンを意味し、その濃度はフッ素イオン電極を有
するメータで処理液を測定することにより求められる。The surface treatment agent (surface treatment bath) of the present invention is preferably 1 to 50 parts by weight (1 to 50 ppm), preferably 3 to 20 parts by weight (3 to 50 ppm).
20 ppm) of effective fluorine ions. When the content of effective fluorine ions is less than 1 part by weight (1 ppm),
Almost no etching reaction of aluminum occurs, and no film is formed. On the other hand, if it exceeds 50 parts by weight (50 ppm), the etching rate of aluminum will be higher than the rate of film formation, making it difficult to form a film. Moreover, even if a film is formed, resistance to boiling water blackening and adhesion to the coating film will deteriorate. Here, effective fluorine ions mean free fluorine ions, and the concentration thereof is determined by measuring the treatment liquid with a meter having a fluorine ion electrode.
有効フッ素イオンの供給源としては、ＨＦ、 Ｎｌｔ、
Ｆ、ＮＩｌ、ＨＦ２、ＮａＰ ５ＮａＨＦ２などを挙げ
ることができ、特にＨＰが好ましい。Effective sources of fluorine ions include HF, Nlt,
Examples include F, NIl, HF2, NaP5NaHF2, and HP is particularly preferred.
また、本発明の表面処理浴はｐ＋＋が１．８〜４．０、
好ましくは２．６〜３．２であることが必要である。Further, the surface treatment bath of the present invention has a p++ of 1.8 to 4.0,
It is preferably between 2.6 and 3.2.
ｐＨが１．８未満では、アルミニウムのエツチング反応
が大きくなりすぎて、皮膜が生成し難くなり、また４、
０を越えると、Ｚ＋”Ｍ−ＡＩ−ＰＯｎの沈澱が生じ易
くなる。If the pH is less than 1.8, the etching reaction of aluminum becomes too large and it becomes difficult to form a film.
When it exceeds 0, precipitation of Z+''M-AI-POn tends to occur.
本発明の表面処理剤（表面処理浴）には、必要に応じて
、グルコン酸く塩）、ヘプトン酸（塩）などのようなア
ルミニウムの有機キレート剤を添加してもよい。The surface treatment agent (surface treatment bath) of the present invention may optionally contain an organic chelating agent for aluminum such as gluconic acid (gluconic acid salt), heptonic acid (salt), and the like.
本発明の表面処理剤は、上述の各成分を水に添０
加混合して水性濃厚溶液にすることにより調製されるが
、これを適量の水で所定濃度に希釈後、必要に応じて所
定のｐ＋＋に調整し本発明の表面処理浴とする。The surface treatment agent of the present invention is prepared by adding and mixing each of the above-mentioned components to water to form a concentrated aqueous solution. After diluting this with an appropriate amount of water to a predetermined concentration, The surface treatment bath of the present invention is prepared by adjusting p++ to .
本発明の表面処理浴をアルミニウム又はその合金に適用
するには、浸漬法、スプレー法、絞りロール法などの任
意の処理方法を用いることができ、一般に室温〜５０℃
、好ましくは３０〜４０℃の温度で適用処理する。また
、処理時間は、処理方法、処理温度によっても異なるが
、通常、５〜６０秒という極めて短い時間で処理が完了
する。To apply the surface treatment bath of the present invention to aluminum or its alloy, any treatment method such as a dipping method, a spray method, or a squeeze roll method can be used, and generally from room temperature to 50°C.
, preferably at a temperature of 30-40°C. Although the processing time varies depending on the processing method and processing temperature, the processing is usually completed in an extremely short time of 5 to 60 seconds.
本発明の表面処理浴が適用されるアルミニウム又はその
合金としては、アルミニウム、アルミニウムー銅合金、
アルミニウムーマンガン合金、アルミニウムーマグネシ
ウム合金、アルミニウムマグネシウム−ケイ素合金、ア
ルミニウムー亜鉛合金、アルミニウムー亜鉛−マグネシ
ウム合金などを挙げることができ、板、棒、線、管など
の任意の形で処理することができる。特に、アルミニウ
ム製飲料缶を処理するのが適している。Examples of aluminum or its alloy to which the surface treatment bath of the present invention is applied include aluminum, aluminum-copper alloy,
Examples include aluminum-manganese alloy, aluminum-magnesium alloy, aluminum-magnesium-silicon alloy, aluminum-zinc alloy, aluminum-zinc-magnesium alloy, etc., and can be processed into any form such as plate, rod, wire, tube, etc. I can do it. It is particularly suitable for treating aluminum beverage cans.
本発明の表面処理浴でアルミニウム又はその合金を処理
すると、アルミニウムが有効フッ素によりエツチングさ
れ、処理浴中に存在する選択された金属、ジルコニウム
、リン酸、フッ素とで複塩を形成し、強固な皮膜を生成
する。ジルコニウムは選択された金属の析出促進剤とし
て作用すると推定される。また皮膜面に塗装印刷を施す
と皮膜と塗膜との密着性が著しく大きくなるが、これは
選択された金属と塗膜との相互作用によるものと考えら
れる。このように本発明においては、選択された金属イ
オン、ジルコニウムイオン、リン酸イオン及び有効フッ
素イオンの相互作用により、良好な耐食性、耐沸水黒変
性、滑り性等を有する皮膜が得られる。When aluminum or its alloy is treated with the surface treatment bath of the present invention, the aluminum is etched by effective fluorine, forming a double salt with the selected metal, zirconium, phosphoric acid, and fluorine present in the treatment bath, and forming a strong Produces a film. It is assumed that zirconium acts as a precipitation promoter for selected metals. Furthermore, when the surface of the coating is painted and printed, the adhesion between the coatings increases significantly, and this is thought to be due to the interaction between the selected metal and the coating. As described above, in the present invention, a film having good corrosion resistance, resistance to boiling water blackening, slipperiness, etc. can be obtained through the interaction of selected metal ions, zirconium ions, phosphate ions, and effective fluorine ions.
以下、実施例及び比較例により本発明を更に詳細に説明
する。Hereinafter, the present invention will be explained in more detail with reference to Examples and Comparative Examples.
なお、以下の実施例及び比較例における（１）耐沸水黒
変性、（２）塗膜密着性、（３）滑り性は、下記のよ
１−
２
うに評価した。In addition, (1) boiling water blackening resistance, (2) coating film adhesion, and (3) slipperiness in the following examples and comparative examples are as follows.
Rated 1-2.
（１）耐沸水黒変性
表面処理浴で処理したアルミニウム缶を乾燥し、その缶
から底部を切り出して、１００℃の水道水に３０分間浸
漬した後の黒変度を下記の５段階で評価する。(1) Dry an aluminum can that has been treated with a boiling water resistant blackening surface treatment bath, cut out the bottom of the can, immerse it in tap water at 100°C for 30 minutes, and then evaluate the degree of blackening on the following 5 scales. .
◎ ：まったく黒変なし
○ ：わずかに黒変
△ ：軽い黒変
× ：かなり黒変
××：完全に黒変
（２〕塗膜密着性
表面処理浴で処理したアルミニウム缶を乾燥し、その缶
の外面にエポキシ−フェノール系塗料（東洋インキ■製
フィニシーズＡ）を塗布、焼付硬化して試験片とする。◎ : No blackening at all ○ : Slight blackening △ : Light blackening × : Significant blackening × × : Completely blackening (2) Dry the aluminum can treated with the paint film adhesion surface treatment bath, and remove the can. An epoxy-phenol paint (Finisees A manufactured by Toyo Ink ■) is applied to the outer surface of the specimen, and the specimen is hardened by baking to obtain a test piece.
この２枚の試験片の間に、厚さ４０μｍのポリアミド系
フィルム（ダイセル化学工業＠製ダイ了ミドフィルム＃
７０００）をはさんで加熱圧着後、幅５ ｉｎｎの試験
片を切り出し、Ｔ型ピール法及び１８０° ピール法で
剥離強度を測定する。単位はｋｇｆ１５ｍｍで表わす。Between these two test pieces, a polyamide film with a thickness of 40 μm (Daicel Chemical Industry
7000), and then cut out a test piece with a width of 5 inches, and its peel strength was measured using the T-peel method and the 180° peel method. The unit is kgf15mm.
なお、そのまま測定したものを一次密着性、９０℃の水
道水に７．５時間浸漬した後測定したものを二次密着性
とする。The primary adhesion is measured as is, and the secondary adhesion is measured after being immersed in tap water at 90° C. for 7.5 hours.
（３）滑り性
第１図に示すように、傾斜角θを変更できるようにした
滑り板１に、２つの表面処理アルミニウム缶２．２′を
、底部が互いに逆を向き、圧延目が水平方向となるよう
に両面テープで固定し、その缶２．２′の上に、缶２．
２′と直交するように２つの表面処理アルミニウム缶４
．４′を載置する。その際、缶４．４′の底部５．５′
を互いに逆向きに配置し、圧延目は垂直方向になるよう
にする。また、上の２つの缶４．４′は、下の缶２．２
′と接触しない側面部で両面テープにより互いに固定さ
れている。(3) Sliding properties As shown in Fig. 1, two surface-treated aluminum cans 2 and 2' are placed on a sliding plate 1 whose inclination angle θ can be changed, with the bottoms facing oppositely to each other and the rolling eyes horizontal. Fix with double-sided tape so that the direction is the same, and place can 2.2' on top of can 2.2'.
Two surface-treated aluminum cans 4 perpendicular to 2'
．． 4' is placed. At this time, the bottom 5.5' of the can 4.4'
are arranged in opposite directions to each other so that the rolling lines are in the vertical direction. Also, the upper two cans 4.4' are the lower cans 2.2'.
They are fixed to each other with double-sided tape at the side parts that do not come into contact with .
滑り板１をおこして、傾斜角θを大きくしていき、上の
２つの缶４．４′が滑り始めたときの角度θを測定し、
ｔａｎθから摩擦係数を算出する。摩擦係数の値から、
次の５段階評価を行 ３−
４
つ。Raise the sliding plate 1, increase the inclination angle θ, and measure the angle θ when the upper two cans 4 and 4' start to slide.
Calculate the friction coefficient from tanθ. From the value of friction coefficient,
Give the following five-point rating: 3-4.
◎ ：０．７未満
○ ：０．７以上 ０．８未満
△ ：０．８以上 ０，９未満
Ｘ ： ０．９以上 １，０未満
ｘｘ：１．０以上
実施例１〜２５
アルミニウム板（Ｊ Ｉ Ｓ Ａ３００４）に絞り−し
ごき加工を施して得られた缶本体を、酸性クリーナ（日
本ペイント株式会社製、商品名サーフクリナーＮ ＨＣ
１００）でスプレー脱脂し、水洗後、第１表に示した組
成及びｐＨの表面処理浴で４０℃にて３０秒間スプレー
処理した。次いで、水洗及び脱イオン水による洗浄を行
い、オーブン中で２００℃で乾燥した。乾燥後の缶につ
いて、耐沸水黒変性、塗膜密着性及び滑り性を測定、評
価した。結果は第２表に示す通りであった。◎: Less than 0.7 ○: 0.7 or more, less than 0.8 △: 0.8 or more, less than 0.9 The can body obtained by drawing and ironing the JIS A3004) was washed with an acidic cleaner (manufactured by Nippon Paint Co., Ltd., trade name: Surf Cleaner N HC).
100), and after washing with water, spray treatment was performed at 40° C. for 30 seconds in a surface treatment bath having the composition and pH shown in Table 1. Then, washing with water and deionized water was performed, and drying was performed in an oven at 200°C. After drying, the cans were measured and evaluated for boiling water blackening resistance, paint film adhesion, and slipperiness. The results were as shown in Table 2.
第
■
表
（
続
き
）
１６一
第
２
表
（
続
き
）
１３−
第
表
注二（１） Ｌａ （ＮＯ，） ３・６Ｈ，０として添
加（２） （ＮＨ４） ＪｒＦｓとして添加（３） １
１．Ｐｏ、とじて添加
（４） ＩＩＩ’として添加
（５） ｐｌ（の調整はｌｌＮＯ３及びアンモニア水に
より行った。Table ■ (Continued) 16-Table 2 (Continued) 13- Table Note 2 (1) La (NO,) Added as 3・6H,0 (2) (NH4) Added as JrFs (3) 1
1. Added as Po (4) Added as III' (5) pl (adjustment was performed with 11NO3 and aqueous ammonia.
第１表
注
（１）各金属イオンは硝酸塩として添加（２） （Ｎ
Ｈ４） ２１ ｒ Ｆ、どして添加（３）８３ＰＯ４と
して添加
（４，） ＨＦとして添加
（５）ｐＨの調整はＨＮ ０３及びアンモニア水により
行った。Notes to Table 1 (1) Each metal ion is added as a nitrate (2) (N
H4) 21 r F, added as (3) 83 Added as PO4 (4,) Added as HF (5) Adjustment of pH was performed with HN 03 and aqueous ammonia.
比較例１〜８
比較のために、第３表に示す組成及びｐ＋＋の表面処理
浴を調製した。これらの表面処理浴を用いて実施例１と
同様にアルミニウド缶の表面処理を行った。次いで実施
例１と同様に各種試験を行った。Comparative Examples 1 to 8 For comparison, surface treatment baths having the compositions and p++ shown in Table 3 were prepared. Using these surface treatment baths, aluminum cans were surface treated in the same manner as in Example 1. Next, various tests were conducted in the same manner as in Example 1.
結果を第４表に示す。The results are shown in Table 4.
第
表
以上の結果から明らかなように、本発明の表面処理浴で
処理した場合（実施例１〜２５）は、耐沸水黒変性、塗
膜との密着性、滑り性共に良好な結果が得られる。選択
された金属イオンが１０ｐｐｍ（１，０重量部）未満の
場合（比較例１及び７）は、耐沸水黒変性、塗膜密着性
、滑り性がいずれも不良である。また、ジルコニウムイ
オンが１０ｐｐｍ（１９重量部）未満の場合（比較例２
及び８）及び有効フッ素イオンがｌｐｐｍ（１重量部）
未満の場合は（比較例４）は、満足な皮膜が形成されず
、耐沸水黒変性、塗膜密着性、滑り性のいずれもが不良
である。As is clear from the results in Table 1 and above, when treated with the surface treatment bath of the present invention (Examples 1 to 25), good results were obtained in terms of boiling water blackening resistance, adhesion to the paint film, and slipperiness. It will be done. When the selected metal ion is less than 10 ppm (1.0 parts by weight) (Comparative Examples 1 and 7), the boiling water blackening resistance, coating film adhesion, and slipperiness are all poor. In addition, when the zirconium ion content is less than 10 ppm (19 parts by weight) (Comparative Example 2
and 8) and effective fluorine ion is lppm (1 part by weight)
If it is less than (Comparative Example 4), a satisfactory film is not formed, and all of the boiling water blackening resistance, film adhesion, and slipperiness are poor.
更に、リン酸イオンが１０ｐｐｍ（１０重量部）未満の
場合（比較例３）は、耐沸水黒変性、塗膜密着性が劣っ
たものとなる。ｐＨが１．８未満の場合（比較例５）は
、皮膜が生威し難いため、わずかに黒変が生じ、塗膜密
着性も悪い。一方、ｐ＋＋が４．０を越える場合（比較
例６）は、処理浴に沈澱が生じ、白濁して耐沸水黒変性
がやや劣り、塗膜密着性も悪くなる。Furthermore, when the phosphate ion content is less than 10 ppm (10 parts by weight) (Comparative Example 3), the resistance to boiling water blackening and coating film adhesion are poor. When the pH is less than 1.8 (Comparative Example 5), the film is difficult to survive, resulting in slight black discoloration and poor coating film adhesion. On the other hand, when p++ exceeds 4.0 (Comparative Example 6), precipitation occurs in the treatment bath, which becomes cloudy, resulting in slightly poor boiling water blackening resistance and poor coating film adhesion.
本発明の表面処理剤（表面処理浴）によれば、低温、短
時間で極めて耐食性の高い皮膜をアルミニウム又はその
合金の表面に形成することができる。この皮膜は沸とう
水中に浸漬しても黒色化せず、低皮膜量でも優れた耐沸
水黒変性を示す。また、皮膜上に塗装印刷を施す場合、
非常に強固な塗膜密着性を得ることができる。更に、皮
膜面が良好な滑り性を有しているため、缶の搬送を行う
うえで極めて有利である。According to the surface treatment agent (surface treatment bath) of the present invention, a highly corrosion-resistant film can be formed on the surface of aluminum or its alloy in a short time at low temperature. This film does not turn black even when immersed in boiling water, and exhibits excellent boiling water blackening resistance even with a low film amount. In addition, when applying paint printing on the film,
Very strong coating adhesion can be obtained. Furthermore, since the coated surface has good slip properties, it is extremely advantageous for transporting cans.
本発明の表面処理剤（表面処理浴）は処理液の濃度が多
少変動しても十分な性能を得ることができるので、処理
液の管理が容易になるという利点も有している。The surface treatment agent (surface treatment bath) of the present invention has the advantage that sufficient performance can be obtained even if the concentration of the treatment liquid changes somewhat, so that the treatment liquid can be easily managed.
以上のような特徴を有する本発明の処理剤は特にアルミ
ニウム製缶の表面処理に好適である。The treatment agent of the present invention having the above characteristics is particularly suitable for surface treatment of aluminum cans.
第１図は、滑り性の測定方法を説明するための斜視図で
ある。
１・・・・・・・・・・・滑り板FIG. 1 is a perspective view for explaining a method of measuring slipperiness. １・・・・・・・・・・・・Sliding board
Claims (2)
オジム、ネオジム、サマリウム、ユーロピウム、ガドリ
ウム、テルビウム、ジスプロシウム、ホルミウム、エル
ビウム、ツリウム、イッテルビウム、ルテチウムからな
る群から選ばれた１種又は２種以上の金属のイオン１０
〜１０００重量部に対して、ジルコニウムイオンを１０
〜５００重量部、リン酸イオンを１０〜５００重量部、
及び有効フッ素イオンを１〜５０重量部の割合で含有す
ることを特徴とするアルミニウム又はその合金の表面処
理剤。(1) Ions of one or more metals selected from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium 10
~1000 parts by weight, 10 zirconium ions
~500 parts by weight, 10 to 500 parts by weight of phosphate ions,
and effective fluorine ions in a proportion of 1 to 50 parts by weight, a surface treatment agent for aluminum or its alloy.
オジム、ネオジム、サマリウム、ユーロピウム、ガドリ
ウム、テルビウム、ジスプロシウム、ホルミウム、エル
ビウム、ツリウム、イッテルビウム、ルテチウムからな
る群から選ばれた１種又は２種以上の金属のイオンを１
０〜１０００ｐｐｍ、ジルコニウムイオンを１０〜５０
０ｐｐｍ、リン酸イオンを１０〜５００ｐｐｍ、有効フ
ッ素イオンを１〜５０ｐｐｍ含み、ｐＨが１．８〜４．
０であることを特徴とするアルミニウム又はその合金の
表面処理浴。(2) Ions of one or more metals selected from the group consisting of scandium, yttrium, lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium. 1
0 to 1000 ppm, 10 to 50 zirconium ions
0 ppm, 10 to 500 ppm of phosphate ions, 1 to 50 ppm of effective fluorine ions, and a pH of 1.8 to 4.
1. A surface treatment bath for aluminum or its alloy, characterized in that:
Priority Applications (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1199656A JPH0364485A (en) | 1989-08-01 | 1989-08-01 | Surface treating agent and treating bath for aluminum or aluminum alloy |
| CA002022254A CA2022254A1 (en) | 1989-08-01 | 1990-07-30 | Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method |
| US07/561,420 US5104577A (en) | 1989-08-01 | 1990-08-01 | Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method |
| EP90114767A EP0411609B1 (en) | 1989-08-01 | 1990-08-01 | Surface treatment chemicals and bath for aluminum or its alloy and surface treatment method |
| DE90114767T DE69005223T2 (en) | 1989-08-01 | 1990-08-01 | Chemical composition and bath for the treatment of surfaces made of aluminum or aluminum alloys, and methods for surface treatment. |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1199656A JPH0364485A (en) | 1989-08-01 | 1989-08-01 | Surface treating agent and treating bath for aluminum or aluminum alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0364485A true JPH0364485A (en) | 1991-03-19 |
Family
ID=16411459
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1199656A Pending JPH0364485A (en) | 1989-08-01 | 1989-08-01 | Surface treating agent and treating bath for aluminum or aluminum alloy |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US5104577A (en) |
| EP (1) | EP0411609B1 (en) |
| JP (1) | JPH0364485A (en) |
| CA (1) | CA2022254A1 (en) |
| DE (1) | DE69005223T2 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028291A1 (en) * | 1996-02-05 | 1997-08-07 | Nippon Steel Corporation | Surface-treated metallic material with corrosion resistance and surface treatment used therefor |
| US6190780B1 (en) | 1996-02-05 | 2001-02-20 | Nippon Steel Corporation | Surface treated metal material and surface treating agent |
Families Citing this family (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5328526A (en) * | 1992-04-03 | 1994-07-12 | Nippon Paint Co., Ltd. | Method for zinc-phosphating metal surface |
| US7294211B2 (en) | 2002-01-04 | 2007-11-13 | University Of Dayton | Non-toxic corrosion-protection conversion coats based on cobalt |
| JP4205939B2 (en) * | 2002-12-13 | 2009-01-07 | 日本パーカライジング株式会社 | Metal surface treatment method |
| DE10314700A1 (en) * | 2003-03-31 | 2004-10-14 | Behr Gmbh & Co. Kg | Method for producing surface-modified workpieces |
| JP4242827B2 (en) * | 2004-12-08 | 2009-03-25 | 日本パーカライジング株式会社 | Metal surface treatment composition, surface treatment liquid, surface treatment method, and surface-treated metal material |
| US8673091B2 (en) * | 2007-08-03 | 2014-03-18 | Ppg Industries Ohio, Inc | Pretreatment compositions and methods for coating a metal substrate |
| US9574093B2 (en) * | 2007-09-28 | 2017-02-21 | Ppg Industries Ohio, Inc. | Methods for coating a metal substrate and related coated metal substrates |
| US9428410B2 (en) | 2007-09-28 | 2016-08-30 | Ppg Industries Ohio, Inc. | Methods for treating a ferrous metal substrate |
| US8097093B2 (en) | 2007-09-28 | 2012-01-17 | Ppg Industries Ohio, Inc | Methods for treating a ferrous metal substrate |
| US8282801B2 (en) * | 2008-12-18 | 2012-10-09 | Ppg Industries Ohio, Inc. | Methods for passivating a metal substrate and related coated metal substrates |
| US9347134B2 (en) * | 2010-06-04 | 2016-05-24 | Prc-Desoto International, Inc. | Corrosion resistant metallate compositions |
| ES2924127T3 (en) | 2012-08-29 | 2022-10-04 | Ppg Ind Ohio Inc | Lithium-containing zirconium pretreatment compositions, associated methods for treating metal substrates, and related coated metal substrates |
| BR112015004358B1 (en) | 2012-08-29 | 2021-05-25 | Ppg Industries Ohio, Inc | method for coating a metal substrate and pretreatment composition for treating a metal substrate |
| CN105026615A (en) | 2013-03-06 | 2015-11-04 | Ppg工业俄亥俄公司 | Methods for treating a ferrous metal substrate |
| US9273399B2 (en) | 2013-03-15 | 2016-03-01 | Ppg Industries Ohio, Inc. | Pretreatment compositions and methods for coating a battery electrode |
| KR20190043155A (en) | 2016-08-24 | 2019-04-25 | 피피지 인더스트리즈 오하이오 인코포레이티드 | Alkaline compositions for treating metal substrates |
Family Cites Families (14)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| NL201472A (en) * | 1952-04-03 | |||
| US3752708A (en) * | 1971-08-23 | 1973-08-14 | Heatbath Corp | Corrosion resistant composition and method |
| CA1098253A (en) * | 1976-04-05 | 1981-03-31 | Timm L. Kelly | Zirconium/titanium coating solution for aluminum surfaces |
| JPS5424232A (en) * | 1977-07-26 | 1979-02-23 | Nippon Packaging Kk | Surface treating method of aluminum |
| FR2417537A1 (en) * | 1978-02-21 | 1979-09-14 | Parker Ste Continentale | COMPOSITION BASED ON HAFNIUM TO INHIBIT CORROSION OF METALS |
| US4187127A (en) * | 1978-12-07 | 1980-02-05 | Nihon Parkerizing Co., Ltd. | Surface processing solution and surface treatment of aluminum or aluminum alloy substrate |
| EP0021602B1 (en) * | 1979-06-07 | 1984-03-14 | Mb Group Plc | Treatment of tin plate surfaces against sulphide staining |
| GB2057300B (en) * | 1979-08-23 | 1982-11-17 | Atomic Energy Authority Uk | Sources for spraying liquid metals |
| US4273592A (en) * | 1979-12-26 | 1981-06-16 | Amchem Products, Inc. | Coating solution for metal surfaces |
| JPS56136978A (en) * | 1980-03-26 | 1981-10-26 | Showa Alum Ind Kk | Chemically treating solution for aluminum or aluminum alloy |
| CA1228000A (en) * | 1981-04-16 | 1987-10-13 | David E. Crotty | Chromium appearance passivate solution and process |
| EP0112826B1 (en) * | 1982-07-12 | 1988-12-28 | Ford Motor Company | Alkaline resistant phosphate conversion coatings and method of making |
| DE3423990A1 (en) * | 1983-07-19 | 1985-01-31 | Omi International Corp., Warren, Mich. | PEROXIDE-FREE CHROME (III) PASSIVATION SOLUTION AND METHOD FOR PASSIVATING SUBSTRATES WITH THIS SOLUTION |
| US4863526A (en) * | 1986-07-11 | 1989-09-05 | Pilot Man-Nen-Hitsu Kabushiki Kaisha | Fine crystalline thin wire of cobalt base alloy and process for producing the same |
-
1989
- 1989-08-01 JP JP1199656A patent/JPH0364485A/en active Pending
-
1990
- 1990-07-30 CA CA002022254A patent/CA2022254A1/en not_active Abandoned
- 1990-08-01 US US07/561,420 patent/US5104577A/en not_active Expired - Fee Related
- 1990-08-01 DE DE90114767T patent/DE69005223T2/en not_active Expired - Fee Related
- 1990-08-01 EP EP90114767A patent/EP0411609B1/en not_active Expired - Lifetime
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1997028291A1 (en) * | 1996-02-05 | 1997-08-07 | Nippon Steel Corporation | Surface-treated metallic material with corrosion resistance and surface treatment used therefor |
| US6190780B1 (en) | 1996-02-05 | 2001-02-20 | Nippon Steel Corporation | Surface treated metal material and surface treating agent |
Also Published As
| Publication number | Publication date |
|---|---|
| DE69005223D1 (en) | 1994-01-27 |
| EP0411609B1 (en) | 1993-12-15 |
| DE69005223T2 (en) | 1994-05-11 |
| CA2022254A1 (en) | 1991-02-02 |
| EP0411609A3 (en) | 1992-07-08 |
| US5104577A (en) | 1992-04-14 |
| EP0411609A2 (en) | 1991-02-06 |
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